Agent for making textiles crease proof and textiles treated by such agent

ABSTRACT

AN AGENT FOR CREASE PROOFING TEXTILES CONTAINING AT LEAST PARTLY CELLULOSE AND/OR REGENERATED CELLULOSE FIBERS IS USED IN AN ORGANIC SOLUTION OF HYDROCARBONS OR CHLORINATED HYDROCARBONS AND IS PRODUCED FROM A MIXTURE CONTAINING SPECFIC PROPORTIONS OF A WATER SOLUBLE METHYLOL COMPOUND OF UREA OR CYCLIC ALKYLENE UREA, THE METHYLOL GROUPS OF WHICH CAN BE ALKOXYLATED, WATER, A SPECIFIC EMULSIFYING AGENT AND POSSIBLY HYDROCARBONS OR CHLORINATED HYDROCARBONS, WHEREBY A CATALYST IS ADDED TO THIS MIXTURE WHICH IS DILUTED WITH HYDROCARBON OR CHOLRINATED HYDROCARBONS TO FORM SOLUTIONS OR FINELY DISPERSED WATER/OIL EMULSIONS WHICH ARE USED FOR THE TEXTILE TREATMENT.

United States Patent 3,565,846 AGENT FOR MAKING TEXTILES CREASE PROOF AND TEXTILES TREATED BY SUCH AGENT Heinz Enders, Stadtbergen, near Augsburg, Wilhelm Dantauello and Giinter Pusch, Leitershofen, near Augsburg, and Siegfried Adolph, Haunstetten, near Augsburg, Germany, assignors to Chemische Fabrik Pfersee G.m.b.H., Augsburg, Germany, a corporation of Germany No Drawing. Filed July 26, 1967, Ser. No. 656,064 Claims priority, application Germany, July 30, 1966, C 39,765; Dec. 24, 1966, C 41,062 Int. Cl. D06m 13/14, 13/38 US. Cl. 260-29.4 Claims ABSTRACT OF THE DISCLOSURE An agent for crease proofing textiles containing at least partly cellulose and/or regenerated cellulose fibers is This invention relates to a crease proofing agent for textiles, particularly those containing at least partly cellulose and/or regenerated cellulose fibers and to textiles treated by such agent.

For a long time, textiles with cellulose or regenerated cellulose fibers have been made crease resistant, shrink resistant and resistant against swelling by treatment with aqueous solutions of aminoplast pre-condensates of various types; or, conventionally, other compounds have been used which form synthetic resins with acid or acid forming hardening agents, this treatment being followed by drying and possible afterheating.

It is also conventional to produce such finishing with washing baths which contain water and an organic solvent miscible with water.

Thus according to US. Pat. No. 3,043,719 textiles are treated by baths which in addition to a pre-condensate which reacts with the fiber and a catalyst, contain a small quantity of water and a large quantity of solvents the acetone or methyl-ethylketone group. This process has the drawback of the volatility and combustibility of such solvents.

When the bath contains larger quantities of water, as for example, is disclosed in British Pat, No. 971,047, considerable fiber expansion is produced, as well as other etfects resulting from working in an aqueous medium.

French Pat. No. 1,174,859 describes a process of crease proofing textiles by a treatment with aqueous solutions of aminoplast forming compounds and hardening agents to which 6 to 17% of organic solvent is added, which is not soluble in water or soluble only to a small extent. This is a two-phase mixture and the solvent is supposed to assist penetration of solid tissues by the aqueous bath.

Essentially the same procedure is described in Ex- "ice ample 13 of British Pat. No. 537,971. This process refers in principle also to treatments with aqueous baths, whereby the fibers go over into a swollen state. The organic liquid used as a separate phase can result in a non-uniform finish.

Finally, according to Austrian Pat. No. 242,096, textiles are made crease proof by the application of synthetic resin pro-condensates having a cross-linking effect with a water content required to make up 3 to 10% of the fabric weight and at the same time an acid or alkaline cross-linking catalyst in a non-aqueous solution or in an emulsion in a neutral organic solvent is used. According to this process the fabric is not impregnated with a bath in the usual manner, but is merely treated with a limited amount of bath which must be precisely dosed. This requires special apparatus.

An object of the present invention is to eliminate the drawbacks of prior art agents.

Other objects will become apparent in the course of the following specification.

In the accomplishment of the objects of the present invention it was discovered that a crease proofing agent can be used which comprises water-soluble methylol compounds of urea or of cyclic urea with their methylol compounds optionally alkoxylated by monovalent saturated alcohols with from 1 to 5 carbon atoms, in solvents which are immiscible with water, namely, liquid hydrocarbons such as benzine or toluol, and particularly in chlorinated hydrocarbons, such as perchloroethylene or carbon tetrachloride in conjunction with the usual acid or acid separating hardening catalysts, particularly those belonging to the group of water-soluble salts or strong acids with bivalent metals, organic amines or ammonia.

Suitable agents are diluted with hydrocarbons or chlorohydrocarbons and are applied jointly with the catalysts, consist of homogeneous mixtures of about 25-60% N-methylol urea possibly alkoxylated, 25-65% water, 10-35% of an emulsifier of the type which will be described hereinafter and possibly 035% hydrocarbon or chlorohydrocarbon solvents (weight percentages).

As pre-condensates high methylolated ureas were found to be suitable, while those with about 1.5 methylol groups are not as satisfactory. Particularly suitable are methylol compounds of cyclic alkylene ureas with 5- to 6-mernbered rings. Also usable are alkoxylated products of all these methylol ureas with low monovalent alcohols.

These pre-condensates may also contain small quantities (about 10 to 20% by weight) of a methylol melamine, which may be alkoxylated. If the contents are higher, usable emulsions cannot be produced, just as in the case with methylol melamines themselves.

The emulsifying agents used must be miscible with resin and have an HLB index of from 3 to 13, with a preferred range being 3 to 8.5. This HLB index according to Griffin (J. Soc. Cosm. Chem. 1949, 311) indicated the hydrophilic-lipophilic equilibrium of an emulsifying agent. In the case of an HLB value below 9 lipophilic properties will predominate, while in the case of a value above 11 the hydrophilic properties will predominate. In accordance with the present invention, with respect to the emulsifying agents with HLB index of 11 to 13, some ionogenic emulsifying agents which are wash active substances are particularly suitable. Hereby miscible means a behavior where mixtures are forming in which no phase separation takes place.

The chemical constitution of the emulsifying agent, namely, whether it is non-iogenic, anion-active or cationactive, is of secondary importance as far as the present invention is concerned.

As .examples of suitable emulsifying agents, together with their HLB index, reference is made to oleic acid monoethanolamide with 7 ethoxy groups (9.4), stearic acid monoethylamide with 7 ethoxy groups (9.5), coconut fatty acid propanol amide with 4 ethoxy groups (7.8), glycerinmonocaprinate (3.5), the polyglycolethers of dodecylamine with 3 ethoxy groups (7.8), stearic acid triethanolaminoester with 2 ethoxy groups (3.5), also sodium salt of dodecylsulphuric acid ester (7.5), the alkaline salt of dodecylbenzene-sulphonic acid (11) or that of a mineral oil sulphonate (7). Emulsifying agents which by themselves do not show the characteristics according to the invention can also be combined into homogenous mixtures with the required HLB index and mixing property with a resin and then become usable. Such mixtures consist for example, of equal parts of polyglycol ether of cetyl and stearyl alcohol with ethoxy groups each (7.2) or ethoxylated oleic acid monoethanolamide with ethoxylated dodecylamine (8.8), of sodium salt of dodecylbenzene-sulphonic acid with nonylphenolpolyglycolether (1113), lorol polyglycolether with 2 ethoxy groups and the sodium salt of the sulphuric acid ester of this polyglycolether (1113), or the acetate of distearyldiethylenetriamide and the formiate of coconut fatty acid amide (7).

The hardening catalysts suited for use in the required agent belong to the familiar hardening catalysts used for crease proof finishing in aqueous baths and are used in quantities of 625% by weight referred to the methylol compounds, and must not, however, interfere with formation of water/oil emulsions. As particularly suitable, were found to be to 60% aqueous solutions of zinc chloride or zinc nitrate, as well as hydrochloride of 2- amino-Z-methylpropanol; however, magnesium chloride or ammonium salts are also suitable.

The agents in the present invention can be produced in any desired sequence. Generally, the methylol compounds and the emulsifying agent are uniformly mixed, then the catalyst is added and then a solvent is added with good stirring for the formation of a homogenous mass. This method is preferably used when the methylol compounds are viscous or paste-like and dissolve only slowly in the solvent.

In certain cases it is advisable to stir initially a solution of the emulsifying agent in a solvent with a catalyst or its concentrated aqueous solution and then to combine the homogenous mixture with the methylol compounds.

Then these mixtures can be diluted with the above mentioned insoluble solvents to become almost clear to opalescent respectively finely dispersed stable water/oil emulsions which can serve as treatment baths. These mixtures contain at least 50% of the above-mentioned solvent and mostly 75 to 90% thereof, depending on the intended mode of application.

Textiles impregnated by such baths are finished by removing the excess bath material, drying them, and subjecting them to after-heating at temperatures of 110 to 170 C. They have excellent crease proof properties which are partly greater than those which can be obtained by aqueous baths of the same synthetic resins and catalyst concentrations, but obviously without the emulsifying agent, and under the same finishing conditions. This process has the added advantage of saving energy during the drying and permitting the finishing of very delicate fabrics which would lose gloss or shape during impregnation with aqueous baths.

In addition to the crease proofing agents of this invention and catalysts, suitable softening agents, fillers or Water proofing agents or oil repelling agents can be used at the same time. The baths which are thus produced are suitable for treatment of textile materials of any kind 4 made of cellulose and/or regenerated cellulose fibers, as well as their mixtures with wool, silk, rayon-acetate and all fully synthetic fibers.

Machines can be used which are suited for the treatment of textiles by non-aqueous baths, which are equipped with recovery devices for organic solvents or which can be combined with such devices. Machines used in the so-called chemical dry cleaning also are practical. However, the textiles can also be sprayed with slightly diluted crease proofing agents of this invention which will make removal of larger quantities of the solution unnecessary.

The following examples are given by way of exemplification only:

EXAMPLE 1 1000 gr. of clear, aqueous 50% solution of dimethylolpropylene urea are mixed uniformly with 350 gr. of an approximately emulsifying agent with the base of oleic acid monoethanolamide and ethoxylated with 7 glycolether-residue. Prior to preparation of the finishing bath cm. of a 50% aqueous solution of zinc chloride set at a pH of 1.5 by hydrochloric acid are stirred in and by adding about 8.5 liters of perchlorethylene, 10 liters of bath are produced. This is a very fine-particled stable emulsion.

White, mercerized cotton poplin with 128 gr. weight per sqm. can be treated by this bath on a suitable machine by impregnation, removal of excess bath, drying in stretched condition and condensation at a C. temperature for 4 minutes. It will show excellent crease-resistant qualities in dry and good crease-resistant qualities in a wet state with relatively good preservation of resistance to tearing.

The following table shows that by finishing in the customary manner in aqueous medium by using the same cross-linking agent in the same concentration and the same catalyst, poorer results are obtained:

A homogeneous mixture of 1000 gr. of a liquid, aqueous 43% dimethylol-dihydroxyethylene urea solution and 200 gr. of the emulsifying agent described in Example 1 is prepared. This product is used to make the finishing bath with gr. of a 50% aqueous zinc nitrate solution which has been adjusted to a pH of 1.0 by means of hydrochloric acid and by addition of about 8.7 liters perchlorethylene to make up 10 liters. This creates a stable, opalescent bath.

When a fine-thread cotton satin is foularded with this bath, dried and condensed at 145 C. for 5 minutes, it will have excellent dry crease resistance with soft feel and its gloss will remain unaffected in contrast to corresponding finishing with an aqueous bath.

EXAMPLE 3 1000 gr. 75% dimethylolglyoxalmonourein are stirred with 300 gr. ethoxylated octadecylamine containing 7 glycolether residue and having an HLB index of 10.8 into a homogenous mixture. It contains 58% of the precondensate, 23% emulsifying agent and 19% water. Then ml. of a 40% aqueous solution of ammonium nitrate can be stirred in and trichlorethylene used to dilute to 10 l.

Dilution is possible also by perchlorethylene or benzine; however, in the case of the latter emulsion formation does not take place as readily. In this case 1500 ml. benzine are initially added While using a high speed mixer and the emulsion thus obtained can then readily be diluted by benzine to a 1. treatment bath.

When a fine-thread cotton satin is foularded by this bath, dried and condensed at 145 C. for 5 minutes, it will have excellent dry crease resistance with soft feel and its gloss will remain undiminished, in contrast to the corresponding treatment by an aqueous bath.

For purposes of application parts by weight of a aqueous solution of crystallized magnesium nitrate can be mixed in and then diluted into a water-in-oil emulsion with trichlorethylene. This can be used, for example, for finishing batiste made of viscose-staple fibers and 50% polyester fibers with very good results.

EXAMPLE 4 1000 gr. of a 30% aqueous solution of a mixture of equal parts of monoand dimethylolethylene urea are mixed with 400 gr. ethoxylated coconut fatty acid propanolamide containing 4 ethoxy groups. To this solution 150 gr. of a 40% aqueous magnesium nitrate solution can be added and the mixture can be diluted to 10 liters by being stirred in perchloroethylene, whereby a colloidal solution is produced which is suited for crease proof finishing.

EXAMPLE 5 A similar usable agent is obtained by mixing a aqueous solution of dimethyloldihydroxyethylene urea with 300 gr. ethoxylated stearic acid monoethylamide containing about 7 ethoxy groups. It can be used with monoethanolaminohydrochloride as a hardening agent in a chlorohydrocarbon solvent.

EXAMPLE 6 Similarly usable is a mixture obtained from 1 kg. dimethylolproplyene urea (70%) and 0.27 kg. of a mixture of equal parts of polyglycol ether of cetyland stearylalcohol with 5 glycol ether groups each, which has an HLB index of 7.2. From this homogenous mixture, which contains 55% pre-condensate, 21% of emulsifying agent and 24% of water, an emulsion is obtained following the admixture of 0.16 kg. of a 50% aqueous zinc chloride solution, and this emulsion can be thinned by benzine to produce a suitable treatment bath.

EXAMPLE 7 A suitable product is also obtained by mixing with a speed mixer 1000 gr. dimethylolglyoxalmono-urein 300 gr. of a 50% aqueous solution containing formiate of coconut fatty acid amide and acetate of stearic ac1d amide of dlethylenetrramlne and 300 gr. trichlor-ethylene. The emulsifying agent used has an HLB index of 7. ml. of concentrated aqueous solution of ammonium nitrate are stirred into this emulsion and it can be used for treatment of textiles following dilution by trichlor-ethylene.

EXAMPLE 8 1000 gr. of a 50% aqueous solution of dimethylol-urea about half of which was alkoxylated by methanol and 300 gr. of an 80% sodium salt of dodecylbenzenesulphonic acid (HBL index 12) provide a mixture of 38% methylol compound, 19% emulsifying agent and 42% water. By using 2-amino-2-methylpropanol hydrochloride as hardening agent it can be utilized in an emulsion prepared in perchloroethylene.

EXAMPLE 9 1000 gr. of a pasty product containing 45% dimethylolurea and 5% of pentamethylolmelamine extensively alkoxylated by methanol is mixed with 200 gr. of an emulsifying agent consisting of a mixture of equal parts of the sodium salt of lorol sulphuric acid ester and lorol polyglycolether with about 7 ethoxyl groups and having an HLB index of 12, and with 200 gr. toluol, using a high speed mixer. The resulting emulsion contains 36% methylol compound, 14% emulsifying agent, 36% water and 14% solvent, and is mixed with monoethanolaminohydrochloride as hardening agent; it can be diluted by toluol prior to application.

EXAMPLE 10 1000 gr. of a 56% aqueous solution of dimethyloldihydroxyethylene-urea is uniformly mixed with 350 gr. of a stearic acid triethanolamine ester containing 2 glycol ether groups and having an HLB index of 3.5. Into this homogenous mixture which contains 41.5% pre-condensate, 26% emulsifying agent and 32.5% water, ml. of a 50% aqueous solution of zinc chloride can be stirred in. Then about 8.5 l. perchloroethylene or benzine are added to make 10 l. A very fine-particled stable emulsion will then result. The emulsion made with perchloroethylene is particularly stable.

White, mercerized cotton poplin with 128 gr. per sqm. Weight can be treated by this bath in a suitable machine by impregnation, squeezing out of the excess bath, drying in stretched condition and condensation for 4 minutes at C. temperature. The treated fabric will show excellent crease proofing elfects in the dry state and good crease proofing effects in the wet state with good tear resistance preservation.

It is apparent that the examples described above have been given solely by way of illustration and not by way of limitation and that they are capable of many variations and modifications within the scope of the present invention. All such variations and modifications are to be included within the scope of the present invention.

What is claimed is:

1. An agent for the crease proofing of textiles containing at least partly cellulose or regenerated cellulose fibers, said agent comprising a mixture of (1) 25 to 60 parts by weight of a water soluble methylol compounds of urea or cyclic alkylene urea with more than 1.5 methylol groups per mol, 25 to 65 parts by weight of water and 10 to 35 parts by weight of an emulsifying agent soluble in hydrocarbons or chlorinated hydrocarbons which is miscible with the methylol compound and having an HLB index of 3 to 13, and (2) at least 50 percent of an organic water insoluble solvent.

2. An agent in accordance with claim 1, wherein the methylol groups of said methylol compound are alkoxylated by monovalent saturated alcohols with 1 to 5 carbon atoms.

3. An agent in accordance with claim 1, wherein said HLB index is from 3 to 8.5.

4. An agent in accordance with claim 1, wherein said methylol compound is derived from cyclic alkylene ureas with 5- to 6-membered rings.

5. An agent in accordance with claim 1, wherein said mixture includes methylol melamine, said methylol melamine replacing from 10 to 20 percentage by weight of said methylol urea compound.

6. A process for crease proofing textiles containing at least partly cellulose or regenerated cellulose fibers with N-methylol compounds of amino-plast forming product in organic solvents by the addition of an acid or an acid-forming catalyst and an emulsifying agent, which comprises saturating the textiles with opalescent or finely dispersed stable diluted 'water-in-oil emulsions consisting of a mixture of 25 to 60 parts by weight of a water soluble methylol compound of urea or cyclic alkylene urea with more than 1.5 methylol groups per mol, 10 to 35 parts by weight of an emulsifying agent soluble in hydrocarbons or chlorinated hydrocarbons which is miscible with the methylol compound and having an HLB index of 3 to 13 7 and 25 to 65 parts by weight of water; '6 to 25 percent by weight of a hardening catalyst referred to the methylol compound and hydrocarbons or chlorinated hydrocarbons, the finishing bath containing at least 50 percent of said organic Water insoluble solvent, and then drying the textiles.

7. A process in accordance with claim 6, wherein said catalyst is a hardening catalyst consisting of a zinc salt or magnesium salt of a strong acid.

8. A process in accordance with claim 6, wherein said catalyst is a hardening catalyst consisting of 2-amino-2- methyl-propanolhydrochloride.

9. A process in accordance with claim 6, wherein the finishing bath contains 75 to 90 percent of said solvent.

10. A textile containing at least partly cellulose or regenerated cellulose fibers and treated by the process of claim 1.

References Cited UNITED STATES PATENTS JOHN C. BLEUTGE, Primary (Examiner US. Cl. X.R.

Notice of Adverse Decision in Interference In Interference No. 97,974 involving Patent No. 3,565,846, H. Enders, W'. Dantanello G. Pusch and S. Adolph, AGENT FOR MAKING TEXTILES GREASE PROOF AND TEXTILES TREATED BY SUCH AGENT, final judgment adverse to the patentees was rendered Nov. 8, 1972, as to claims 1, 2, 3, 4, 6, 7 and 10. 

